Intumescing composition composed of a nitrogen phosphorus compound with an aldehyde resin



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5D Eiiliiillibt annulus iQE Morris L.

poration of Delaware Ni elsen, Dayton, Ohio, assignor to Monl'fmlcal Company, St. Louis, Mo, a cor- No Drawing. Application December 30, 1948, Serial No. 68,406

1 7 Claims.

This invention is directed to fire-resistant compositions having utility as surface coatingsand in various manufactured. articles which are to be protected against fire and the propagation of flames. It is an objedtbfthe invention to provide organic compositions based upon nitrogen-containing resins, which would otherwise burn very easily, but which, by means of the improvement of the present'invention, are able to resist the propagation of a flame. It is another object of the invention to provide resinous or plastic products for various purposes in which a substantially flameproof material is desired. A further object is the preparation of coating compositions utilizing nitrogen-containing resins of the aminoplast type to adapt such resinous materials to treatment for the purpose of rendering the final coating resistant to flame propagation.

Many attempts have been made in the past to provide fireproof coating compositions and resins or plastics, but so far as is known, no plastic of the aminoplast type has previously been made which was successful as a permanent fiameproof or fire-retarding substance. Compositions which have previously been tested have shown only short-time protection in resisting burning and have generally shown poor stability and weathering qualities.

Ammonium phosphate in various form has been. utilized in various fire-retardant compositions, but this material has the disadvantage of retaining its crystalline qualities so that coating compositions or plastic materials utilizing the same have been characterized by a rough, grainy finish. In addition, the water-solubility of the ammonium phosphates have rendered such compositions undesirable, since the property of resisting fire is greatly reduced or completely eliminated as the ammonium phosphates Wash out or weather away from the composition, leaving only organic materials which burn freely.

It has now been found that fire-retarding compositions of great stability may be provided by the combination of an aminoplast resin and certain chemical compounds containing nitrogen and phosphorus. The nitrogen-phosphorus-containing component may be a condensation product of ammonia and phosphoryl chloride. One type of such compounds is described by Mellor in {Joinprehensive Treatise on Inorganic and Theoretical Chemistry, 8, 713 (Longmans, Green and Com pany, New York, 1928). A. preferred compound obtainable from thereaction product of ammonia and phosphoryl chloride by heat treatment thereof is the insoluble,

infusible composition which has been designated as polyphosphorylamide. The preparation of the water-insoluble polyphosphorylamide is described in copending application, Serial Number 68,402, filed December 30, 1948, which application is assigned to the same assignee as is the present application. carried out by passing gaseous ammonia into a solution of phosphorus oxychloride (also called phosphoryl chloride) dissolved in a hydrocarbon solvent boiling above 200 C. until at least 5 moles of ammonia per mole of phosphorus oxychloride have been added and combined therewith. It has been found that a definite compound is formed at this stage, although more ammonia may be added. The reaction is best carried out at temperatures below C. and preferably above 20 0., utilizing normal pressure or elevated pressure. Since exothermic reaction heat is liberated it is desirable to cool the hydrocarbon solution during the reaction in order to maintain the temperature thereof between the above limits. The product formed by this initial reaction is a fine, white powder which consists of a mixture of a nitrogen-phosphorus containing body and ammonium chloride. The nitrogenphosphorus containing body is at this stage watersoluble and alkaline in reaction. If desired, the reaction product may now be separated byfiltration or by centrifuging from the hydrocarbon and the separated product treated according to the second step of my process.

Preferably the heating step may be carried out upon the reaction product produced by the first step while the product is still suspended or mixed with the original hydrocarbon solvent. This results in better yields and simplified operaticn, since the material may be handled more easily and Without losses. The second step of my process involves heating the product produced in the first step to a temperature above C., but below a temperature of 250 0., either at atmospheric or superatrnospheric pressure. During the heating period, a small amount of ammonia is evolved which may be recovered and reused in the process. During the heating step the nitrogen-phosphorus product apparently undergoes a polymerization or molecular rearrangement, being converted thereby into ,a water-insoluble product of higher molecular weight.

Example A One hundred parts of phosphoryl chloride was dissolved in 300 parts of kerosene of commercial grade. The kerosene had a boiling range of about Siltitilifi KUU IP The process is most conveniently 150 to 260 C. Anhydrous ammonia gas was then passed into the kerosene solution at a slow rate of addition, and simultaneously therewith, the solution was cooled in order to maintain the temperature below about 80 C. At the same time, eflicient agitation of the solution Was maintained. The addition of ammonia was continued in this manner until 5 moles of ammonia had been reacted with the phosphoryl chloride. The reaction product was insoluble in kerosene and appeared as a white powder suspended therein.

After completion of the ammonia addition, the reaction mixture, while remaining suspended in kerosene, was heated to a temperature of 200 C.

After the temperature had reached 200 0., heat- 1 ing was discontinued and the mixture permitted to cool. During the heating period; some ammonia was evolved, the nitrogen-phosphorus product apparently undergoing polymerization and becoming water insoluble. At the end of the heating period, which may be carried out for a period of from one-fourth to three hours, preferably one to three hours, the solids were removed from the kerosene by filtration or centrifuging. The product was next washed with water in sufficient amount so as to dissolve the ammonium chloride present the product. The washing operation may also be followed by a heating step which is designed to dry the product and also to remove traces of the kerosene or other hydrocarbon. A convenient method for removing the hydrocarbon consists in steaming the product while it is contained in a rotating centrifuge.

The nitrogen-phosphorus containing product, resulting from the present process, is substantially insoluble in water as well as organic solvents. It may be suspended or dispersed in water and will then exhibit a pH which is substantially neutral or alkaline in reaction. The final product is free from chlorine as a result of the heating and polymerization step, Whichmakes it possible for the ammonium chloride to be completely removed to leave only the condensation product consisting essentially of nitrogen, oxygen, hydrogen and phosphorus. The nitrogen-phosphorus atomic ratio is approximately 1.80:1, but may be varied within the range of 1.5:; to 2.0: 1 by variation of the amount of NH3 initially reacted with the P0013 and this product to some degree polymerized, and then; subjected to heating as de- 1 described above, to complete the polymerization. The polyphosphorylamide is a white powder, insoluble in water, and havinga substantially neutral' or alkaline reaction. The nitrogen-phosphorus atomic ratio of the polymeric material lies in the range of 1.72:1 to 1.80:1, which relatively high range represents a product desirable in providing a composition which, in the presence of nitrogen-containing resins such as aminoplasts, bulks up by releasing nitrogen compounds as gases when exposed to fire.

Polyphosphorylamide per se is infusible except when exposed to a very great heat. It has been found that at high temperatures, such as that resulting from the application of a. flame, the polyphosphorylamide present in the combination resinous composition of the invention reacts chemically with an aminoplast resinous base to generate a non-burning gas which permeates and swells the coating film to form a porous, insulating layer. This action, which is termed intumes-.

" to fire, exhibit the property of intumescing or frothing during thermal decomposition in such a manner that a porous, crusty, solid film or residue is produced. Such porous, crusty film, or residue is suificiently continuous and adherent so that combustible material coated therewith is effectively protected against access of air with the resuit that combustion thereof is greatly diminished and in many cases, completely suppressed. Moreover, the frothy or porous nature of the film or crust considerably retards the transmission of heat into the combustible material, upon which it is supported or coated, so that distillation of combustible'gaseous products is materially diminished, resulting in many cases in the ultimate extinction of fire.

The nitrogen-phosphorus-containing product, which is one component of the preferred composition, is obtained by the reaction of F001;: and ammonia, as described in the above reference to Mellor. It is therein termed diamido diphosphoric acid. However, it may be of somewhat variable composition, depending upon the proportions of the reacting ingredients employed in producing it. Ammonium chloride is uniformly a by-product in the reaction between POCls and ammonia, generally corresponding in amount to all of the chlorine present in the POClz. Such by-product ammonium chloride may be permitted to remain in the ultimate composition or it may be removed, which is generally done by leaching with water, as is described by Mellor.

The product obtained when POCh and ammania are reacted together in the manner described by Mellor generally possesses acidic properties and for many purposes is undesirable for this reason. I, therefore, prefer to use the product made according to the pending application of John E. Malowan and Forest R. Hurley, entitled Composition of Matter and Process for Same, i Serial Number 68,402, filed December 30, 1948, which application is assigned to the same assignee as is the present'case. According to the said Malowan and Hurley invention, the reaction between POC13 and ammonia is preferably carried out in an organic solvent which has a normal boiling point in excess of 200 C., after which the product, While still suspended in the organic solvent, is subjected to a temperature above C. for a'period of time'so that the water-soluble condensation product initially formed is rendered water-insoluble. At the same time,'it has been found that the acidic reaction possessed by the prior art products has been, by the Malowan-I-Iurley process, considerably diminished, the final product possessing'a neutral to slightly alkaline reaction. For application to combustible materials which are normally acid sensitive, the Malowan-Hurley product is accordingly preferred. However, for those combustible products where the acidity of the coating composition is not important, I may use' the POCla-am- UMUQO oiliiiiiifi ascaosv monia reaction products produced according to the prior art processes mentioned above.

The certain nitrogenous or aminoplast condensation products which may be resin-forming are essentially nitrogenous, resinous products suchas the formaldehyde condensation products, preferably of urea or melamine. Specifically, these products may be monoor dimethylol urea or mono-, di-, tri-, tetra-, penta-, or hexa-methylolmelamine. Other condensation products of this type, which may be used in the present compositions, are described in C. Ellis, Chemi try Of Synthetic Resins, chapter 26 (Reinhold Publishing Co., 1935). Examples are the formaldehyde condensation products with urea, melamine, thiourea, guanidine, cyanamide, dicyandiamide, aniline, ptol-uenesulfonamide, and also the corresponding acct-aldehyde and furfural condensation products in the same relationship. Such resinous compositions may employ high, medium or low degrees of methylolation (or the corresponding a'cetal or furfural substituents) such, forexample, as from 1 to 5 methylol radicals per moleof the acceptor compound in the case of melamine. The use of the alkylated modifications of such resins is likewise contemplated, particularly in the butylated modifications such as are conventional in ureaformaidehyde and melamine-formaldehyde resins. Mixtures of such resins, or the addition of other types of resins, may also be carried out.

The fireproofing composition is -pl'ep'ared'mere ly by mixing together the POCh-ammonia reaction product and'th'e urea or melamine-formaldehyde condensation product. A mixture may be made of any of these ingredients in the dry state or the mixture may be produced in aqueous solution or dispersion, or it maybe produced in solution or dispersion in any suitable organic solvent or vehicle.

The proportions may also be varied over a wide range depending upon the degree of fire-retarding efiect desired. It has been found, however, that the essential composition consisting of the POCls-ammonia reaction product and the aminoplast, such as the urea or melamine formaldehyde condensation product, should contain at least parts, and preferably not more than 99 parts, by weight of said PO'Cliammonia condensation product per 100 par is 'by weight of the final mixture. 7

A preferred embodiment of the present invention is provided by utilizing, in conjunction with the aminoplast, the polypho'sphorylami'de 'or'other reaction products of phosphoryl chloride and ammonia, as described by Mellor, supra, in the concentration range of 10% to% by weight of the dry components. High proportions of the phosphorus compound may be employed since this'substance also'acts as a pigmenting agent, which is .particularly advantageous in making white and other light-colored coatings and manufactured articles.

In accordance with the invention, it is contemplated that the products may be applied to the surface of wood or other combustible materials, or non-combustible materials, to provide a film or layer of the aminoplast resin in combination with the phosphorus compound to give a coating which is adherent, stable and weather-resistant. When this material is subjected to heat, a chemical reaction occurs between the phosphorus compound and the nitrogen-containing resin to release gases which intum-esce or puii up the decomposition products to provide a porous, adherent, solid froth or char, which is an excellent heat-insu1ator, and thereby protects the base material or treated surface.

Organic binders, such as chlorinated rubber, chlorinated paraffin, and alkyd resins or polyvinyl chloride, are also optional ingredients in the coating composition or manufactured article, based upon the present plastic materials. The utilization of these binders aids in the application of the material when in a liquid or paste form.

Iilustrative of the combination of the amino type of resin, together with the reaction product of phosphoryl chloride and ammonia, the following examples show certain embodiments of the invention without, however, being limitative of the scope of the invention:

Example 1 A melamine formaldehyde intermediate-stage resin (Melmac) was mixed with 10% by weight, based upon the resin, ofpolyphosphorylami de. The product which was obtained as a granular paste resists combustion, and when appliedwithout further solvents as a coating material to combustible surfaces such as wooden panels, showed no tendency to glow after removal of a test flame. The material was tested in thestandard fire test as described in the American Paint Joural Convention Daily, pages 830, November 6, 1946, which test was modified by the substitution of a gas micro burner for the alcohol cup. The combination product described above showed vigorous inturnescing action when subjected to fire. Under such circumstances, the intumesc'ent material pufied up and released gases to form a porous, heat-insulating char which protected the base material. from the fire.

In general, the proportion of polyph'o'sphorylamide or other reaction products of phosphoryl chloride and ammoniamay be utilized in intumescing compositions in a concentration range of 5 to 50% by weight, based upon the weight of the aminoplast resin employed in the composition.

Example 2 To a solution of 25 parts of polyvinyl chloride in 220 parts of cyclohexanone, there was added 8 parts of polyphosphorylamide and 24 part of urea-formaldehyde molding powder. This combination product was brushed on a wooden-panel as a thin coating and then allowed to dry. When exposed to fire under standard test conditions, this coating intumesced to prevent the wood panel from. burning.

Various resinous constituents, in addition to the polyvinyl chloride illustrated above, may be utilized together with the aminoplast resin such as the urea-formaldehyde employed in this example.

Example 3 Ten parts of polyphosphorylamide employed as a fine, white powder was mixed with 3 0 parts of urea-formaldehyde molding powder. This mixture was then dispersed in a liquid form of a silicone resin, 2. hydrolytic product of organosilicon oxychloride, as described in R. L. Wakemans Chemistry of Commercial Plastics, pages 758-761 (Reinhold Publishing Corporation, 1947).

The above formulation was found to be a noncombustible material which, in the presence of fire, intumesced to form ap'orous, heat insulating char. Various silicone resins, whether in liquid or solid form, may be utilized in the intumesci-ng compositions of the present invention.

The compositions of the invention may be made KUUIW- in the form of a solid in massive form or granulated, and may also be utilized as paste or liquid resin in which the polyphosphorylamide is dispersed. Pigments, dyes, or other coloring materials may also be added if desired. The compositions of the present invention may be utilized in the manufacture of various articles of manufacture or may be applied to wood, paper fabric, leather, rubber and other combustible materials. However, the compositions are also suitable for application to copper, brass and other metals without danger of corrosion. A particularly important application of the compositions of the present invention is to provide a fire-retarding coating composition upon steel. In such applications, the materials applied as a surface coating are free from the danger of flashing, which is char acteristic of most organic coating compositions. In addition, such treated surfaces, when subjected to a high temperature, will not propagate a flame, but instead, will intumesce or swell to provide a heat-insulating, fire-retarding composition. Such treated steel surfaces retain their strength during attack by fire, thereby preventing buckling. The resinous compositions of the invention, when employed as a coating'composition, may be applied in any convenient manner, such as by spraying, brushing, and dipping.

This application contains subject matter in common with certain other applications assigned to the same assignee as is the present application: Serial No. 68,402, filed December 30, 1948, relating to the water-insoluble composition of matter resulting from the reaction of phosphoryl chloride and ammonia;

Serial No. 68,403, filed December 80, 1948, relating to a water-paint comprising a dispersion of the water-insoluble reaction product of phosphoryl chloride and ammonia in combination with water-soluble, nitrogen-containing, resinous materials;

Serial No. 68,404, filed December 30, 1948, relating to a fia-meproofing treatment for cotton by the application thereto of the water-insoluble reaction product Of phosphoryl oxychloride and ammonia;

Serial No. 68,405, filed December 30, 1948, relating to compositions comprising pheno1-formaldehyde resins in combination with the water-insoluble reaction product of phosphoryl chloride and ammonia;

Serial No. 68,407, filed December 30, 1948, relating to water paints based upon the combination of the Water-insoluble reaction product of phosphoryl chloride and ammonia together with water-soluble alkyd resins derived from the reaction of citric acid and glycerine;

Serial No. 68,408, filed December 30, 1948, relating to water emulsion paints comprising the combination of a nitrogencontaining resin and the water-insoluble reaction product of phosphoryl chloride and ammonia together with polyhydroxy compounds such as pentaerythritol;

Serial No. 68,409, filed December 30, 1948, relating to a coating composition comprising an organic solvent containing organic, film-forming resins in combination with the water-insoluble reaction product of phosphoryl chloride and ammonia;

Serial No. 68410, filed December 30, 1948, relating to the combination of the Water-insoluble reaction product of phosphoryl chloride and am monia together with chlorinated rubber;

Serial No. 68,411, filed December 30, 1948, relating to flameproofed cloth having deposited 8 thereon the combination of the water-insoluble reaction product of phosphoryl chloride and ammonia together with antimony oxide and polyvinyl chloride;

Serial No. 136,135, filed December 30, 1949, relating to glowproofing compositions comprising the combination of the reaction product of phosphoryl chloride and ammonia together with antimony oxide and chlorinated paraflins;

Serial No. 136,136, filed December 30, 1949, relating to compositions comprising the combination of the reaction product of phosphoryl chloride and ammonia together with compounds having free hydroxy radicals such as pentaerythritol.

Having now described certain specific forms of the invention, it is to be understood that the invention is not to be limited to the specific forms of the compositions herein described or specifical- 1y covered by the claims.

What I claim and desire to protect by Letters Patent of the United States is:

1. An intumescing composition composed of the water-insoluble reaction product of phosphoryL, chloride and anhydrousammonia, said water-insollibl pr'o'duct having a nitrogen/phosphorus ratio between 1.72:1 and 1.80:1, in combination with a resin selected from the group consisting of the reaction products of an aldehyde with a member of the class consisting of urea, melamine and dicyandiamide.

2. An intumescing, fire-retarding composition composed of the water-insoluble reaction product of phosphoryl chloride and anhydrous ammonia, said water-insoluble product having 2. nitrogen/phosphorus ratio between 1.72:1 and 1.80:1, in combination with a resin derived by the reaction of formaldehyde with melamine.

3. An intumescing, fire-retarding composition composed of the water-insoluble reaction product of phosphoryl chloride and anhydrous ammonia, said water-insoluble product having a nitrogen/phosphorus ratio between 1.72:1 and 1.80:1, in combination with a resin derived by the reaction of acetaldehyde with melamine.

4. An intumescing, fire-retarding, coating composition consisting of the water-insoluble reaction product of phosphoryl chloride and anhydrous ammonia, said water-insoluble product having a nitrogen/phosphorus ratio between 1.72: 1 and 1.80: 1, in combination with a urea-formaldehyde resin.

5. An intumescing, fire-retarding, coating composition consisting of the water-insoluble reaction product of phosphoryl chloride and anhydrous ammonia, said water-insoluble product having a nitrogen/phosphorus ratio between 1.72:1 and 1.80:1 in combination with a urea-acetaldehyde resin.

6. An intumescing, fire-retarding composition composed of the water-insoluble reaction product of phosphoryl chloride and anhydrous ammonia, said water-insoluble product having a nitrogen/phosphorus ratio between 1.72:1 and 1.80:1, said reaction product being in combination with a resin selected from the group consisting of the reaction products of an aldehyde with a member of the class consisting of urea, melamine and dicyandiamide in which the said reaction product is present to the extent of 5% to 50% based upon the weight of the said resin.

7. An intumescing fire-retarding composition composed of the water-insoluble product havin a nitrogen/phosphorus ratio between 1.72:1 and 1.80:1, said reaction product being in combination with the condensation product of formaldewuss risriifiiitiji: SEARCH ROOM 2,596,987 9 10 hyde with urea, in which the said reaction prod- Number Name Date not is present to the extent of from 5% to 50% by 2,163,085 Cupery June 20, 1939 weight of the said resinous condensation product. 2,413,163 Bacon Dec. 24, 1946 L MO L NIE SEN FOREIGN PATENTS 5 REFERENCES CITED Number Country Date The following references are of record in the 4 Switzerland Malt 1 m this Patent: OTHER REFERENCES UNITED STATES PATENTS 10 Mellor, Comprehensive Treatise on Inorganic Number Name D t and Theoretical Chemistry, vol. 8 (1928); pages 2,052,886 Leroy Sept. 1, 1936 7 4-72 

1. AN INTUMESCING COMPOSITION COMPOSED OF THE WATER-INSOLUBLE REACTION PRODUCT OF PHOSPHORYL CHLORIDE AND ANHYDROUS AMMONIA, AND WATER-INSOLUBLE PRODUCT HAVIANG A NITROGEN/PHOSPHOURUS RATIO BETWEEN 1.72:1 AND 1.80:1, IN COMBINATION WITH A RESIN SELECTED FROM THE GROUP CONSISTING OF THE REACTION PRODUCTS OF AN ALDEHYDE WITH A MEMBER OF THE CLASS CONSISTING OF UREA, MELAMIE AND DICYANIDIAMIDE. 